Leaf emergences in Microlepis oleaefolia (DC.) Triana (Melastomataceae) and their probable function: an anatomical and ultrastructural study

Microlepis oleaefolia (DC.) Triana, an endemic species of Melastomataceae from the Brazilian cerrado, presents very complex leaf structures called as "hairs with root-like base" embedded in the mesophyll. This paper describes the ontogenesis, histochemical and structural aspects of these leaf structures as a framework for further functional studies. Samples of leaves in different developmental stages were processed according to common light and electron microscopy techniques. Fresh material was subjected to histochemical tests to examine the chemical composition of cell walls. The apoplastic transport between leaf emergences and the vascular system was verified by staining with 1% aqueous safranin. The structures are emergences of mixed protoderm and ground meristem origin. They are persistent, predominantly short-stalked and dendritic. Their arms have thick non-lignified cellulosic walls with a loose and heterogeneous aspect; on the inner face, the wall, which appears labyrinthine, presents small irregularly shaped projections directed towards the protoplast. The base of the emergences is composed of sclereids embedded in the mesophyll that reach the vascular system. Assays with aqueous safranin solution revealed it penetrates the cell walls of the arms and showed a connection between the emergence and xylem. Anatomical, chemical and ultrastructural features of leaf emergences of M. oleaefolia indicate that these structures are able to transport substances via apoplast and can absorb or exude solutions.     

Heavy fermion quantum criticality

During the last few years, investigations of rare-earth materials have made clear that heavy fermion quantum criticality exhibits novel physics not fully understood. In this work, we write for the first time the effective action describing the low energy physics of the system. The f fermions are replaced by a dynamical scalar field whose nonzero expected value corresponds to the heavy fermion phase. The effective theory is amenable to numerical studies as it is bosonic, circumventing the fermion sign problem. Via effective action techniques, renormalization group studies, and Callan-Symanzik resummations, we describe the heavy fermion criticality and predict the heavy fermion critical dynamical susceptibility and critical specific heat. The specific heat coefficient exponent we obtain (0.39) is in excellent agreement with the experimental result at low temperatures (0.4).     

Excitation of pygmy dipole resonance in neutron-rich nuclei via Coulomb and nuclear fields

We study the nature of the low-lying dipole strength in neutron-rich nuclei, often associated with the pygmy dipole resonance. The states are described within the Hartree-Fock plus RPA formalism, using different parametrizations of the Skyrme interaction. We show how the information from combined reaction processes involving the Coulomb and different mixtures of isoscalar and isovector nuclear interactions can provide a clue to reveal the characteristic features of these states.     

The Shapes of Sulfonamides: A Rotational Spectroscopy Study

Benzenesulfonamides are a class of molecules of extreme interest in the biochemical field because many of them are active against a variety of diseases. In this work, the pharmacophoric group benzensulfonamide, its derivatives para-toluensulfonamide and ortho-toluensulfonamide, and the bioactive molecule sulfanilamide, were investigated using rotational spectroscopy to determine their conformations and the influence of different substituents on their structures. For all species, the hyperfine structure due to the ¹⁴N atom was analyzed, and this provided crucial information for the unambiguous identification of the observed conformation of all molecules. In addition, for ortho-toluensulfonamide, the vibration–rotation hyperfine structure related to the methyl torsion was analyzed, and the methyl group rotation barrier was determined. For benzensulfonamide, partial r_S and r₀ structures were established from the experimental rotational constants of the parent and two deuterated isotopic species. In all compounds except ortho-toluensulfonamide, the amino group of the sulfonamide group lies perpendicular to the benzene plane with the aminic hydrogens eclipsing the oxygen atoms. In ortho-toluensulfonamide, where weak attractive interactions occur between the nitrogen lone pair and the methyl hydrogen atoms, the amino group lies in a gauche orientation, retaining the eclipsed configuration with respect to the SO₂ frame. A comparison of the geometrical arrangements found in the PDB database allowed us to understand that the bioactive conformations are different from those found in isolated conditions. The conformations within the receptor are reached with an energy cost, which is balanced by the interactions established in the receptor.     

Synthesis of a New β-Galactosidase Inhibitor Displaying Pharmacological Chaperone Properties for GM1 Gangliosidosis

GM1 gangliosidosis is a rare lysosomal disease caused by the deficiency of the enzyme β-galactosidase (β-Gal; GLB1; E.C. 3.2.1.23), responsible for the hydrolysis of terminal β-galactosyl residues from GM1 ganglioside, glycoproteins, and glycosaminoglycans, such as keratan-sulfate. With the aim of identifying new pharmacological chaperones for GM1 gangliosidosis, the synthesis of five new trihydroxypiperidine iminosugars is reported in this work. The target compounds feature a pentyl alkyl chain in different positions of the piperidine ring and different absolute configurations of the alkyl chain at C-2 and the hydroxy group at C-3. The organometallic addition of a Grignard reagent onto a carbohydrate-derived nitrone in the presence or absence of a suitable Lewis Acid was exploited, providing structural diversity at C-2, followed by the ring-closure reductive amination step. An oxidation-reduction process allowed access to a different configuration at C-3. The N-pentyl trihydroxypiperidine iminosugar was also synthesized for the purpose of comparison. The biological evaluation of the newly synthesized compounds was performed on leucocyte extracts from healthy donors and identified two suitable β-Gal inhibitors, namely compounds 10 and 12. Among these, compound 12 showed chaperoning properties since it enhanced β-Gal activity by 40% when tested on GM1 patients bearing the p.Ile51Asn/p.Arg201His mutations.     

A torsion-based solution to the hyperbolic regime of the $$J_2$$ -problem

A popular intermediary in the theory of artificial satellites is obtained after the elimination of parallactic terms from the \(J_2\)-problem Hamiltonian. The resulting quasi-Keplerian system is in turn converted into the Kepler problem by a torsion. When this reduction process is applied to unbounded orbits, the solution is made of Keplerian hyperbolae. For this last case, we show that the torsion-based solution provides an effective alternative to the Keplerian approximation customarily used in flyby computations. Also, we check that the extension of the torsion-based solution to higher orders of the oblateness coefficient yields the expected convergence of asymptotic solutions to the true orbit.

     

Negishi Cross-Coupling in the Preparation of Benzyl Substituted Pyrrolo[2,3-d]pyrimidine Based CSF1R Inhibitors

The colony-stimulating factor 1 receptor (CSF1R) is a protein kinase emerging as an attractive target with clinical relevance in cancer, CNS and inflammatory diseases. Molecular docking experiments followed by synthesis and structure–activity relationship have been used to identify low molecular weight structures as promising hits for lead optimization. These molecules are synthesized from a 4-chloro-6-iodo-pyrrolo[2,3-d]pyrimidine building block using Negishi and Suzuki–Miyaura cross-coupling reactions in high yields. Several inhibitors possessed excellent enzymatic potency, and the parent compound preferably binds to the autoinhibited form of CSF1R. Cellular and in vivo profiling indicate that further tuning of drug structure is needed prior to efficacy studies.     

eHydrogenation: Hydrogen-free Electrochemical Hydrogenation

Hydrogenation reactions are staple transformations commonly used across scientific fields to synthesise pharmaceuticals, natural products, and various functional materials. However, the vast majority of these reactions require the use of a toxic and costly catalyst leading to unpractical, hazardous and often functionally limited conditions. Herein, we report a new, general, practical, efficient, mild and high-yielding hydrogen-free electrochemical method for the reduction of alkene, alkyne, nitro and azido groups. Finally, this method has been applied to deuterium labelling.     

Natural Eutectic Solvent Mixture of l-Menthol/Malonic acid (4 : 1) and Its Ibuprofen Solution: Thermal and Physical Characterizations and NMR Studies of Molecular Interaction

A eutectic mixture of L-menthol and malonic acid, Me / MA (4 : 1), was characterized by calorimetry and other physical measurements. The new deep eutectic solvent (m.p. 6 °C) solvates 338 mg of ibuprofen per mL, and the solution is stable in a wide temperature range. Strategies of NMR titration used in supramolecular chemistry were employed to explore binding forces between the eutectic constituents as well as solute-solvent interaction in ibuprofen solution. Even in acetonitrile, Me ₄ MA is formed through a hydrogen-bonding network, where the constituents act as hydrogen donors and acceptors at the same time. The estimated association constant is around 30 M⁻¹; the binding forces are enough to build the eutectic mixture at high concentrations. The aggregate Me ₄ MA forms a molecular complex with ibuprofen in acetonitrile as a result of the cooperative effect of the constituents. In addition, van der Waals interactions are operative between ibuprofen and menthol in the saturated IB - Me / MA (4 : 1) solution.     

A simple and fast method for evaluating the athermal limit of semirigid liquid polymers

A simple method is reported allowing the fast evaluation of the athermal limit that is implicitly present within the set of equations recently proposed by Jonah, Brostow and Hess, dealing with the anisotropic‐isotropic equilibria of single monodisperse or nearly monodisperse semirigid liquid polymers, including polymer liquid crystals. We have found an athermal limit dependent on the degree of rigidity θ of the given semirigid liquid polymer (θ being the fraction of its monomeric units belonging to rigid rodlike sequences within each semiflexible polymeric chain) and marked off by critical lengths η_al of the rigid sequences, giving rise to non‐finite asymptotic values of the anisotropic‐isotropic temperatures.